Field of the Invention
The invention relates to methods for patterning ferroelectric layers disposed on semiconductor substrates, as are used in particular for fabricating storage capacitors on large scale integrated FeRAM and DRAM components.
Ferroelectric materials are used for the fabrication of ferroelectric capacitors for applications in nonvolatile semiconductor components having a high integration density, but also for future large scale integrated volatile DRAM semiconductor memory components. The materials are able to maintain an electrical polarization in the absence of an externally applied voltage, for which reason they are used for nonvolatile semiconductor memories. At the same time, the materials also have a very high relative permittivity, for which reason they are of interest for large scale integrated DRAM memory components, for increasing the capacitance of the storage capacitors.
Preferred ferromagnetic materials for semiconductor memories are materials from the perovskite group. Representatives of the perovskite group are crystals having the compound structure ABX3, where A primarily denotes the ions Ca, Ba, Pb, K and rare earths, B denotes ions as Ti, Zr, Sn, Nb, Ta, etc. and X denotes an oxygen atom or a halogen atom. In memory technology, SrBi2Ta2O9 (SBT), Pb(Zr, Ti)O3 (PZT), or Bi4Ti3O12 (BTO), in particular, are used as dielectrics between the plates of a capacitor. These materials have oxygen and no halogen as the third constituent, X3. These materials are applied to the surface and crystallized in a ferro-annealing process step in oxygen at a temperature of around approximately 800xc2x0 C.
A plate material of the capacitors with a ferroelectric dielectric is preferably a noble metal that withstands the high temperatures of the ferro-annealing process step in oxygen or is converted completely or partially into a conductive oxide under these conditions. Appropriate materials for this are primarily Pt, Pd, Ir, Rh, Ru or Os or conductive noble metal oxides such as IrOx, RhOx, RuOx, OsOx, SrRuO3.
In general, capacitor construction in large scale integrated memory components follows the so-called stack principle, in which the capacitor contains a sandwich structure formed by a bottom electrode, a dielectric layer and a top electrode, which is applied on an insulating layer above a selection transistors.
It is accordingly an object of the invention to provide a method of patterning ferroelectric layers that overcomes the disadvantages of the prior art methods of this general type.
With the foregoing and other objects in view there is provided, in accordance with the invention, a first method for patterning a ferroelectric layer on a main surface of a semiconductor substrate. The first method includes the steps of providing the semiconductor substrate having the ferroelectric layer, providing a mask for patterning the ferroelectric layer, carrying out a dry etching process using an etching gas mixture having halogen-containing gases, carrying out a heat treatment process after performing the dry etching process, and feeding H2O to the semiconductor substrate.
With the foregoing and other objects in view there is provided, in accordance with the invention, a second method for patterning a ferroelectric layer on a main surface of a semiconductor substrate. The second method includes the steps of providing the semiconductor substrate having the ferroelectric layer, providing a mask for patterning the ferroelectric layer, carrying out a dry etching process using an etching gas mixture having halogen-containing gases, and carrying out a heat treatment process in an O2-containing atmosphere after performing the dry etching process. A temperature at the semiconductor substrate is about 500xc2x0 C. for about 2 to 4 hours and then is driven up to 650 to 800xc2x0 C.
The methods according to the invention have the advantage that a ferroelectric layer can be patterned without the disadvantages described. Dry etching using etching gas mixtures having halogen-containing gases suppresses fence formation in the mask openings. In this case, the incorporation of halogens into the ferroelectric layer, which is harmful for the ferroelectric layer, is suppressed or reversed by the addition of H2O or O2. The feedback of oxygen into the ferroelectric material, shown using the example of H2O with SBT as the dielectric material, can happen e.g. through the reaction
SrBi2Ta2O9-xHal2x+x H2O xe2x86x92 SrBi2Ta2O9+2HHalx 
where Hal denotes F, Cl, Br and/or I.
The addition of H2O or O2 results principally in the recovery of the electrostatic breakdown strength of the ferroelectric layer, which is of importance in particular when the ferroelectric serves as a dielectric of a storage capacitor and has to withstand electric fields of 5-10xc3x97106 V/m without a significant leakage current.
Furthermore, the adhesive strength of the ferroelectric layer, impaired as a result of the dry etching using halogen-containing etching gases, is re-established as a result of the feeding in of H2O and/or O2. The adhesive strength plays a special part e.g. if the ferroelectric layer is a dielectric between two capacitor electrode layers.
The two methods according to the invention differ in the presence and absence of H2O for annealing the ferroelectric layer. Whereas in the first method, the annealing of the ferroelectric layer degraded by the dry etching is affected by a reaction of H2O with the halogen atoms. According to the second method the annealing is effected by a reaction of O2 with the halogen atoms. In the first method, the annealing is preferably effected in accordance with the chemical sequence:
H2O+2 Halxe2x88x92 xe2x86x922 HHal+Oxe2x88x92 with Hal=F, Cl, Br, I, 
whereas in accordance with the second method the annealing is preferably effected by:
O2+4 Halxe2x88x92 xe2x86x922 Hal2+2 Oxe2x88x92 with Hal=F, Cl, Br, I. 
The exchange of the halogen atoms in the ferroelectric material by the oxygen atoms in accordance with the second method is affected by heat treatment of the semiconductor substrate for 2 to 4 hours at about 500 degrees Celsius, after this time the temperature being driven up to 650 degrees to 800 degrees Celsius. The driving-up process is preferably carried out such that the semiconductor substrate is in the temperature range between 650 and 800 degrees Celsius for about 15 to 30 minutes. The atmosphere during the heat treatment preferably has a pressure of 1 atmosphere. In this case, the atmosphere preferably essentially contains oxygen. Through the heat treatment, the halogen atoms incorporated into the ferroelectric material as a result of the dry etching using the halogen-containing etching gas mixture are exchanged by the oxygen in accordance with the stoichiometric ratio. The method according to the invention furthermore has the advantage that it can be easily integrated into the overall process sequence.
The patterning of the ferroelectric layer takes place as a result of the dry etching step. The dry etching is preferably affected in plasma. The plasma contains an etching gas mixture that has halogen-containing gases and provides for a sufficient etching rate on ferroelectric layers and for a sufficient selectivity. In this case, the mask prescribes the structure of the layer to be patterned. In a preferred embodiment, the mask contains a silicon oxide or a nitride; however, it may also contain a resist which is removed again e.g. after the etching. The mask is preferably applied directly on the ferroelectric layer or on a layer which covers the ferroelectric layer.
The heat treatment step after the dry etching step is carried out in order to anneal the ferroelectric layer that has been exposed to the etching gas mixture and has thus been damaged, and to improve the adhesive strength of the ferroelectric layer with respect to the adjacent layers. The damage caused by the etching gas mixture is affected in particular at edges of the etched regions, since the mask does not cover and protect the ferroelectric layer there. An annealing of the ferroelectric layer, in particular an increased breakdown voltage strength and increased adhesive strength is achieved, however, only if, in accordance with the first method, H2O is added to the substrate during the dry etching step, during the heat treatment step and/or during a stripping process step. In the case of the method in accordance with the second method, the annealing of the ferroelectric layer takes place by a heat treatment in an O2-containing atmosphere.
The methods according to the invention are preferably used when a conductive layer, in particular a conductive layer made of a noble metal or noble metal oxide, is applied on the ferroelectric layer. Both the conductive layer and the ferroelectric layer are then preferably patterned in one process step. Preferred conductive layers are made, in particular, of Pt, Pd, Ir, Rh, Ru, or Os, or of the conductive oxides IrOx, RhOx, RuOx, OsOx, SrRuOx. In particular, this method is used for a Pt layer on a ferroelectric layer. In this case, the dry etching step is able to pattern largely anisotropically the noble metal or noble metal oxide layerxe2x80x94chemically difficult to etchxe2x80x94and the underlying ferroelectric layer in one step. Although in this case the halogen-type gases cause a degradation of the ferroelectric layer with regard to the breakdown voltage strength and the adhesive strength at the opened edge regions, these can largely be compensated for through the addition of O2 during the heat treatment or of H2O during the dry etching, the heat treatment and/or the stripping process.
The ferroelectric layer is preferably made of materials of the perovskite group, in particular materials of the so-called ABO3 class, where O denotes oxygen, and A and B denote metals from the group strontium, calcium, barium, bismuth, cadmium, lead, titanium, tantalum, hafnium, tungsten, niobium, zirconium, scandium, yttrium, lanthanum, antimony, chromium or thallium. SrBi2Ta2O9 (SBT), Pb(Zr, Ti)O3 (PZT) and/or Bi4Ti3O12 (BTO) are particularly preferred. In the crystallized state, these materials are able to maintain an electrical polarization even in the absence of an external voltage (remanence). They are thus suitable as dielectrics for storage capacitors of nonvolatile memories. Furthermore, they are distinguished by a high relative permittivity, for which reason they can also be used as dielectrics for capacitors on very large scale integrated dynamic memories (DRAMs).
In a preferred method, the etching is carried out by a reactive ion etching (RIE) process step or, with further preference, by a magnetic enhanced RIE (MERIE) process step. These methods enable, during the etching, a high degree of anisotropy and thus a high dimensional accuracy of the structure transfer. This is the basic precondition for the fabrication of very large-scale integrated circuits. By virtue of the magnetic plasma densification, the MERIE process step additionally permits a higher etching rate and gentle treatment of the surfaces. The halogens for the halogen-containing gases are preferably Cl2, BCl3 and/or HBr.
In a preferred embodiment in accordance with the first method, the H2O is fed to the semiconductor substrate during the etching operation. This can be done by introducing water vapor or gases which generate H2O in the dry etching reactor into the dry etching reactor, e.g. an MERIE reactor. The H2O passes to the ferroelectric layer in particular at the opened regions of the mask. The annealing of the ferroelectric layer by the H2O takes place in parallel with the patterning in this case.
In a further preferred embodiment, the H2O is fed to the semiconductor substrate during the heat treatment step after the patterning. In the simplest case, this is done by adding water vapor into the atmosphere of the heat treatment furnace, preferably at a heat treatment temperature of between 400xc2x0 C. and 900xc2x0 C. The annealing of the ferroelectric layer takes place principally at the edge regions of the openings of the ferroelectric layer, i.e. the margins and edges of the ferroelectric layer. However, as in the previous case, the H2O can also be fed in by gas mixtures that react chemically to form water only in the heat treatment furnace.
If the mask is a resist that is removed again after the patterning by a stripping process step, then, in a preferred embodiment, the H2O is fed in during the stripping process step. The stripping process step preferably takes place in a process chamber in which the O2 and O3 are converted into plasma, which incinerates the resist. In a preferred embodiment according to the invention, the H2O is fed to the process chamber in the form of water vapor, so that the ferroelectric layer can be annealed at the open regions. In other preferred embodiments, the H2O is also generated only in the process chamber through combustion of hydrogen and oxygen that are fed separately to the process chamber.
In one preferred method, the H2O is transported in each case in the form of water vapor through the substrate in particular to the main surface of the substrate to be patterned. In another preferred method, the H2O is generated by the transporting of H2 and O2 and the subsequent combustion of the two gases on site. In this case, the H2 and/or O2 are/is preferably transported in an inert carrier gas in order to reduce the explosiveness of the gases. In a further preferred method, the hydrogen is transported to the respective reactor through hydrogen-containing compounds or hydrogen-rich volatile organic compounds such as alkanes, cycloalkanes, alkenes, cycloalkenes, alcohols, aldehydes and/or ketones and caused to undergo combustion with the oxygen to form water on site. xe2x80x9cOn sitexe2x80x9d refers to in each case xe2x80x9cin the direct vicinity of the semiconductor substratexe2x80x9d, in particular at the patterned main surface. In the case of H2O being fed during the dry etching step, xe2x80x9con sitexe2x80x9d refers to the H2O being essentially generated in the dry etching reactor; in the case of H2O being fed during the heat treatment, xe2x80x9con sitexe2x80x9d refers to the H2O being essentially generated in the heat treatment furnace; in the case of H2O being fed during the stripping process, xe2x80x9con sitexe2x80x9d refers to the H2O being essentially generated in the process chamber in which the mask is removed.
In a preferred embodiment, the ferroelectric layer forms a part of storage capacitors, the ferroelectric layer being the dielectric and the conductive layer being the top electrode of the storage capacitors. Furthermore, the semiconductor substrate preferably has bottom electrodes that form storage capacitors together with the ferroelectric layer and the top electrode. The bottom electrodes are preferably applied on an insulating layer that electrically insulates the selection transistors on the semiconductor substrate from the bottom electrodes. The capacitors are preferably storage capacitor for DRAM and FeRAM semiconductor memories, the bottom electrodes being electrically connected to selection transistors in a preferred embodiment. In this case, the selection transistors are preferably applied on a silicon, GaAs or Ge substrate.
Other features which are considered as characteristic for the invention are set forth in the appended claims.
Although the invention is illustrated and described herein as embodied in a method of patterning ferroelectric layers, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.